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US4443310A - Photoinitiated synthesis of mercaptans - Google Patents

Photoinitiated synthesis of mercaptans Download PDF

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Publication number
US4443310A
US4443310A US06/357,068 US35706882A US4443310A US 4443310 A US4443310 A US 4443310A US 35706882 A US35706882 A US 35706882A US 4443310 A US4443310 A US 4443310A
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Prior art keywords
process according
reaction medium
initiator
reaction
compound
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US06/357,068
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English (en)
Inventor
Emmanuel Arretz
Claude Landoussy
Alfred Mirassou
Jean Ollivier
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Societe Nationale Elf Aquitaine Production SA
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Societe Nationale Elf Aquitaine Production SA
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Priority claimed from FR8104956A external-priority patent/FR2501679A1/fr
Priority claimed from FR8202849A external-priority patent/FR2521990A2/fr
Application filed by Societe Nationale Elf Aquitaine Production SA filed Critical Societe Nationale Elf Aquitaine Production SA
Assigned to SOCIETE NATIONALE ELF AQUITAINE (PRODUCTION), reassignment SOCIETE NATIONALE ELF AQUITAINE (PRODUCTION), ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: ARRETZ, EMMANUEL, LANDOUSSY, CLAUDE, MIRASSOU, ALFRED, OLLIVIER, JEAN
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
    • C07C319/04—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by addition of hydrogen sulfide or its salts to unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/16—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of hydrogen sulfide or its salts to unsaturated compounds

Definitions

  • the present invention relates to an improved process of production of mercaptans starting from olefinic compounds, by reaction of the latter with hydrogen sulphide. It relates more particularly to a new group of initiators allowing this reaction to be carried out under the effect of ultraviolet radiation.
  • No. 3,050,452 also, although it is necessary according to this patent to utilise ultraviolet of wavelengths shorter than 300 nm, it is possible to operate above 300 nm in the case of benzo- or thiobenzophenones. The results are remarkably improved when these benzophenones and/or thiobenzophenones are employed in conjunction with phosphites or other organic derivatives of elements of Group V A.
  • the present invention provides a notable improvement with respect to all these processes of the prior art, in that it allows a substantial increase in the rate of production of the mercaptan starting from an olefinic compound. It has the advantage of being realizable either without a solvent or in a solvent, such as an organic sulphide, a hydrocarbon or an ether. In the case of an organic sulphide, the advantage is all the more marked as the sulphide can be the one obtained as a by-product in the reaction itself.
  • the new process according to the invention is characterised in that the reaction medium includes a derivative of the xanthene type which acts as an initiator for the formation of the mercaptan starting from an unsaturated compound and H 2 S, under the effect of ultraviolet radiation.
  • the initiators according to the invention correspond to the formula: ##STR1## where Y is O or S, while X designates an element O, S or Se, a --CH 2 , --CH 2 CH 2 --, SO 2 , CO, CS or NR' group, R' being a hydrocarbon radical or even a tri- or pentavalent phosphorus group, particularly ##STR2## where R designates an alkyl, an aryl, an H or a halogen.
  • the symbols R 1 to R 8 designate the same or different atoms or groups, such as H, halogen, alkoxy, alkyl and/or aryl.
  • the preferred range of wavelength is from 300 to 400 nm.
  • the rate of conversion of the olefinic compound into the mercaptan is even higher, if the xanthene derivative is added in conjunction with an organic compound of an element of group V A of the Periodic Classification, known per se as an initiator for the photochemical reaction in question. Low proportions of initiators suffice, which shows that the xanthane derivative exerts a synergistic action with the organic compound of group V A.
  • the xanthene type additive according to the invention can also be a corresponding organic compound of bismuth, arsenic or antimony; for example, alkyl or aryl arsenites or arsines are suitable as additives.
  • the proportions of the xanthane derivative according to the invention to be added to the reaction medium depend upon various factors, particularly the nature of the reactants treated, their concentration in the medium, the presence or absence of a solvent and so on. Most frequently, these proportions are of the order of 0.0001 to 0.1 mole per liter of reaction medium and in particular 0.0003 to 0.001.
  • the proportion of the compound of the element of Group V A is of the same order.
  • the temperatures and the H 2 S/olefin proportions are the same as in the corresponding technique already known from prior publications. It is thus not necessary to describe them in detail here; it will merely be noted that the preferred H 2 S/olefin molar ratios are about 2 to 10, the temperature being maintained between -10° and +20° C., temperatures ranging from -10° to -5° and from +20° to +35° C. nevertheless being utilisable, but less advantageously.
  • the reaction can be carried out at atmospheric pressure, but it is preferable, to accelerate conversion to the mercaptan, to operate at manometric pressures of 3 to 30 bars.
  • esters in question can particularly contain C 1 to C 30 alkyls and more particularly from C 1 to C 8 .
  • the olefinic compounds can include several double bonds, as is the case for example with butadiene or 2,4-hexadiene.
  • the process applies equally to unsaturated compounds carrying substituents, such as halides, hydroxyls, alkoxy groups, carboxyls etc; it can thus be carried out with products such as allyl chloride, allyl alcohol, alkyl or aryl maleates or fumarates and similar compounds.
  • Unsaturated triple bond compounds are also utilisable in the process of the invention; this is particularly the case with alkynes, such as acetylene which produces vinyl-mercaptan.
  • the median ring can contain 6 or 7 elements, the latter configuration corresponding to the presence of --CH 2 CH 2 -- at X; if Y is oxygen, the compound, which in this case is dibenzosuberone, forms in the liquid state and is thus easily manipulable and readily accessible industrially.
  • Y is oxygen
  • X is --CH 2 CH 2 --.
  • a particular advantage of the initiators according to the invention is that if required that can serve under atmospheric pressure; although under these conditions the rate of conversion of the olefin and the hourly production of the mercaptan are less than under a pressure of several bars, they are clearly more effective than the prior initiators, such as organic phosphites alone or acetophenones employed under the same conditions.
  • the absence of secondary products other than the corresponding sulphide allows ready separation of the mercaptan formed and recycling of the olefin and the hydrogen sulphide.
  • the reaction is effected in a cylindrical reactor of stainless steel of 245 ml, equipped with a coaxial quartz tube containing UV lamp, the maximum emission of which corresponds to the wavelength of 350 nm. Cooling and agitation of the reaction medium are ensured by an external circuit, constituted by a recirculation pump and an exchanger which allows the temperature of the reaction medium to be maintained at about 10° C.
  • a series of tests are effected, the following parameters of which are kept constant: hydrogen sulphide supply of 250 l/h, 1-dodecene supply of 336 g/h and a pressure of 12 bars. The particular conditions of each test and the results obtained are given in the following table.
  • benzophenone or thioxanthone are used in association with a phosphite, the rate of which is 19 ⁇ 10 -4 , that of the benzophenone being 33 ⁇ 10 -4 and that of the thioxanthone being 1 ⁇ 10 -4 mole per hour.
  • the apparatus of the preceding examples is used at a temperature of about -3° C. and a pressure of 9 to 10 bars.
  • 100 ml/h of dipropyl sulphide, 10 ⁇ 10 -4 moles/h of thioxanthone and 1.9 ⁇ 10 -3 mole/h of tributyl phosphite are continuously introduced, as well as, in gaseous form, 120 l/h of H 2 S and 60 l/h of propylene.
  • a conversion of 74.8% of the propylene is obtained and a production of 70.3 g/h of n-propylmercaptan.
  • dodecylmercaptan is prepared with, as the initiators, dibenzosuberone (X being --CH 2 CH 2 -- and Y being oxygen) and thiodibenzosuberone (the same X, S atom at Y.)
  • dibenzosuberones like all the xanthenic derivatives of the foregoing examples, employed in much lower doses than the initiators of the known art, give better results than the latter.
  • the photochemical "Pyrex" reactor is of the known type with a submerged coaxial lamp; its glass inlet is fritted at the base to ensure good diffusion of the hydrogen sulphide and propylene gases.
  • the irradiated volume is 90 ml.
  • This reactor thermostated with an external double envelope, operates discontinuously at ambient pressure, the gas inputs being maintained constant throughout the experiment. They are in fact 30 l/h for H 2 S and 30 l/h for propylene.
  • the solvent is the diethyl ether of diethylene glycol and the temperature at which it is saturated with hydrogen sulphide and propylene is 10° C.
  • the photosensitiser concentration corresponds to the optimum of the intensity absorbed in the reactor.
  • the luminous source is a low-pressure mercury lamp of reemission centered at 350 nm. Its power is 8 watts. After 30 minutes, the quantities of mercaptan formed and the percentage of propylene converted are those in the following table.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
US06/357,068 1981-03-12 1982-03-10 Photoinitiated synthesis of mercaptans Expired - Lifetime US4443310A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FR8104956 1981-03-12
FR8104956A FR2501679A1 (fr) 1981-03-12 1981-03-12 Perfectionnement a la synthese photoinitiee de mercaptans
FR8202849 1982-02-22
FR8202849A FR2521990A2 (fr) 1982-02-22 1982-02-22 Perfectionnement a la synthese photoinitiee de mercaptans

Publications (1)

Publication Number Publication Date
US4443310A true US4443310A (en) 1984-04-17

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US06/357,068 Expired - Lifetime US4443310A (en) 1981-03-12 1982-03-10 Photoinitiated synthesis of mercaptans

Country Status (6)

Country Link
US (1) US4443310A (de)
EP (1) EP0060754B1 (de)
BR (1) BR8201327A (de)
CA (1) CA1162510A (de)
DE (2) DE60754T1 (de)
IT (1) IT1150653B (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050040028A1 (en) * 2001-04-05 2005-02-24 Melanie Hebert Semi-continuous photochemical method and device therefor
WO2018049016A1 (en) * 2016-09-12 2018-03-15 Chevron Phillips Chemical Company Lp Methods for producing thiol compounds and sulfide compounds using diphenylamine or a phenol compound
WO2018146415A1 (fr) 2017-02-13 2018-08-16 Arkema France Procédé de préparation de polythiols
EP3992180A1 (de) * 2020-10-29 2022-05-04 Chevron Phillips Chemical Company LP Verfahren zur herstellung von thiolverbindungen und sulfidverbindungen unter verwendung einer monoalkylphenolverbindung

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2608599B1 (fr) * 1986-12-17 1989-03-31 Elf Aquitaine Synthese de dithiols
FR2627184B1 (fr) 1988-02-17 1990-07-13 Elf Aquitaine Procede de preparation de dithiols
US20140221692A1 (en) 2013-02-04 2014-08-07 Chevron Phillips Chemical Company Lp Flow Reactor Vessels and Reactor Systems

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4052283A (en) * 1974-12-23 1977-10-04 Hooker Chemicals & Plastics Corporation Sensitized production of sulfhydryl compounds using ultraviolet radiation
US4233128A (en) * 1978-05-05 1980-11-11 Societe Nationale Elf-Aquitaine (Production) Photosynthesis of mercaptans

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4052283A (en) * 1974-12-23 1977-10-04 Hooker Chemicals & Plastics Corporation Sensitized production of sulfhydryl compounds using ultraviolet radiation
US4233128A (en) * 1978-05-05 1980-11-11 Societe Nationale Elf-Aquitaine (Production) Photosynthesis of mercaptans

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050040028A1 (en) * 2001-04-05 2005-02-24 Melanie Hebert Semi-continuous photochemical method and device therefor
CN100369664C (zh) * 2001-04-05 2008-02-20 阿托菲纳公司 半连续光化学方法及其实施设备
US7491299B2 (en) 2001-04-05 2009-02-17 Arkema France Semi-continuous photochemical method and device therefor
WO2018049016A1 (en) * 2016-09-12 2018-03-15 Chevron Phillips Chemical Company Lp Methods for producing thiol compounds and sulfide compounds using diphenylamine or a phenol compound
US10189779B2 (en) 2016-09-12 2019-01-29 Chevron Phillips Chemical Company, Lp Methods for producing thiol compounds and sulfide compounds using diphenylamine or a phenol compound
KR20190054067A (ko) * 2016-09-12 2019-05-21 셰브론 필립스 케미컬 컴퍼니 엘피 디페닐아민 또는 페놀 화합물을 사용하여 티올 화합물 및 설파이드 화합물을 생산하는 방법
US10501408B2 (en) 2016-09-12 2019-12-10 Chevron Phillips Chemical Company Lp Methods for producing thiol compounds and sulfide compounds using diphenylamine or a phenol compound
EP3753920A1 (de) * 2016-09-12 2020-12-23 Chevron Phillips Chemical Company LP Verfahren zur herstellung von thiolverbindungen und sulfidverbindungen unter verwendung von diphenylamin oder einer phenolverbindung
WO2018146415A1 (fr) 2017-02-13 2018-08-16 Arkema France Procédé de préparation de polythiols
US11999682B2 (en) 2017-02-13 2024-06-04 Arkema France Method for preparing polythiols
EP3992180A1 (de) * 2020-10-29 2022-05-04 Chevron Phillips Chemical Company LP Verfahren zur herstellung von thiolverbindungen und sulfidverbindungen unter verwendung einer monoalkylphenolverbindung

Also Published As

Publication number Publication date
EP0060754A1 (de) 1982-09-22
IT8220066A0 (it) 1982-03-10
DE60754T1 (de) 1983-04-14
IT1150653B (it) 1986-12-17
CA1162510A (fr) 1984-02-21
DE3264185D1 (en) 1985-07-25
BR8201327A (pt) 1983-01-25
EP0060754B1 (de) 1985-06-19

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